Phenol ethers



2,694,737 Patented Nov. 16, 1954 United States Patent '0 Ice (2) OCH;CHz'O 2,694,737 j Al(OR);

OCH OCHzCHiO- GHO+2GHtCHOHC H PHENOL ETHERS 5 OCH: CHaO 0 Louis H. Backand Lewis J. Carlson, Shelton, Wash., asl v H v signors to RayonierIncorporated, Shelton, Wash., in HOOH OCHz'OHzO-.C -H:OH+2CH;-GC4Hvcorporation of Delaware No Drawing. Original application April 24, 1951,Serial No. 222,734, now Patent No. 2,649,436, dated August 18, 1953.Divided and this application .May 7, 1953, Serial No. 353,670

2 Claims. (Cl. 26t)-61'3) Reaction 1 results in the formation of thedialdehyde ethylene divanillin ether which is an important intermediatein the method of this invention.

Reaction 2 results in the formation of the dihydric alcohol which, oncondensation, forms the resins of the said application.

The dihydric alcohols of the invention condense intermolecularly whenheatedt'o form a polymer by splitting This invention relates to organiccompounds and has out water between the hydroxyl groups and nuclearhyfor its ob ect the provision of a new class of dlhydrlc alcodrogenatoms of an adjacent molecule, as illustrated in hols and an efficientand economically advantageous the following reaction:

00m 1130 (|)CH3 orno HO ormGo-R-o-Oorhon H0 ore-Qc-n-o-Oomon O'CfiHz(311:0 Room-Qo-n-o-Ocmon CHaO OCH:

nocnGo-a-o-Oom method of producing the dihydric alcohols. While the Thelinear polymer which is first formed can be furdihydric alcohols of theinvention have general utility, ther condensed by continued heating toeffect the reacthey are advantageously useful for the preparation oftion of the remaining hydroxyl groups to form a crossthermosettingresins as described and claimed in applicalinked infusible resin.

tion Serial No. 222,734, filed April 24, 1951, now U. S. The preparationof compounds of this invention is Patent 2,649,436, of which thisapplicatiolrli is a diVizliOl. illustrated by the following specificexamples:

The so-called thermosetting resins are c aracterize y 4 a cross-linkedor lattice structure and have the property of Example 1 Ethylene dwamllmether being infusible and insoluble in all solvents except those 40 Ithat decompose them. While the thermosetting resins l heretoforeproduced are variously colored or opaque, the 0CH0OH:CHz0-OHO moldedresins of the invention are colorless and clear.

The dihydric alcohols of the invention are represented A mixture f 7parts f vanillin, 212 parts of sodium by the following S tu hydroxide,450 parts of water and 47 parts of ethylene R10 dibromide was placed ina reaction vessel equipped with l l v a mechanical stirring device and areflux condenser. The

mixture was heated .to refluxing and stirred continuously for 21 hours.At. the end of this time a tan-colored granu- In the above formulae, theR-group represents a dilar solid had separated from the reactionmixture. This valent aliphatic chain of 24 carbon atoms which may beproduct when dried had a melting point of 180 184 C. The yield was 67.9parts. It could be crystallized from interrupted by an oxygen-ethergroup and R1 represents methyl or ethyl. Examples of R include thefollowing:

the monomethyl ether of ethylene glycol to give colorless needles withno change in melting point. The product was ethylene divanillin ether.CH2CH2CH2-- CH2CH2CH2-CH2 Example 2.-Ethylene divanillin etherCH2CH2OCH2CH2 A mixture of 76 parts of vanillin, 21.2 parts of sodium 0hydroxide, 450 parts of water, and 30 parts of ethylenedi- One importantaspect of the invention 15 that the starting material for the dihydricalcohols may be vamllin chloride was placed in an autoclave equippedwith a which is potentially available in great abundance by themechanical stirrer. The mixture was heated to 120-130 C. and stirredcontinuously for 4 hours. The gauge presalkaline oxidation of sulfitewaste liquor, a by-product 1n the manufacture of cellulose from wood.

sure was 70 pounds at the start and fell to 50 pounds at the end. Aproduct similar to that of Example 1 was Specific dihydric alcoholsnftalyi be prepared from vanilobtained in a yield f 4 parts 1m by asenes of reactlons as o 0 Example 3.Tetramethylene dzvamllm ether i 0?H3 (IT/H3O I- BrCHrCHzBr 2H0 @0110 aOH OCHOO outsmart-120112000110 0CH3 CHSO A mixture of.76 parts of vanillin, 20 parts of s'odiumhydroxide, 500 parts of water, and 31.8 parts of 1,4-d ichlorobutane wasplaced in an autoclave and stirred 7 I l 00H-Oo omcmo-Oonowmnwzmc) hoursat a temperature of 130-140 C. The maximum gauge pressure was 40 pounds.A solid product was obtained which was recrystallized from 300 parts ofethylene glycol monomethyl ether. Forty parts of a crystalline productmelting at 155160 C. was obtained. The product was tetramethylenedivanillin ether.

Example 4.-Diethylene glycol divanillin ether OfiJ a CHsOoort-OoomcmocmomoO -CHO Example 5.Ethylene-bis-(2-meth0xy-4-hydroxymethylphenyl) ether OCHQ' 31130 HO CH A mixture of parts ofethylene divanillin ether as 1 prepared in Example 1, 403 parts ofmethyl isobutyl carbinol, and 15 parts of aluminum isopropoxide wasplaced in a distilling apparatus equipped with mechanical stirrer and adistilling column packed with glass helices and attached to a totalreflux distilling head. The mixture was stirred and refluxed, and thedistillate was bled' off slowly. The vapor temperature was 81 C. at thestart and 13.5 parts of distillate was obtained at a vapor temperatureof 81-90 C. This represents the isopropanol obtained from the aluminumisopropoxide. The vapor temperature then rose to 115 C. and 88 parts ofdistillate was obtained at a temperature of 115-127 C. This fractioncontained methyl isobutyl ketone obtained from the oxidation of methylisobutyl carbinol. The total refluxing time was 7 hours. The reactionmixture was then placed in a steam distillation apparatus and subjectedto steam distillation until all the methyl isobutyl carbinol had beenremoved. The insoluble residue was then crystallized from water to give27 parts of colorless, crystalline needles having a melting point of132135 C. This product was ethylene bis (2 methoxy 4hydroxymethylphenyl) ether.

Example 6.--Tetramethylene-bis-(2-meth0xy-4- hydroxymethylphenyl) etherHoorrGoomcmomcmoGomon Example7.-Bis-(2-methoxy-4-hydroxymethylphenoxyethyl) ether (|)CH: $H3O nocm-o-oomontoonzomoOcmon This compound was prepared by the proceduredescribed in Example 5, using 12.8 parts of diethylene glycol divanillinether, 5 parts of aluminum isopropoxide, and 250 parts of methylisobutyl carbinol. The product was crystallized from water. .The meltingpoint was 98- Example 8.--C0ndensation of ethylene bis-(Z-methoxy-4-hydr0xymethylphenyl) etherEthylene-bis-(2-methoxy-4-hydroxymethylphenyl) ether was heated 1 hourat a temperature of 175196 C. During the heating there was activeboiling as water was split out during the condensation. The product wasa lowmelting, colorless, resinous solid. It was insoluble in mostsolvents but could be dissolved in dimethyl formamide.

Example 9.' C0ating steel A 25% solution of the product of Example 7 indimethyl formamide and containing 1% oxalic acid was coated on a steelrod, dried in an oven at C., and then baked for 1% hours at 160-170 C.Four successive coatings were applied in this manner. The film wastransparent and had a light amber color. It was resistant to all organicsolvents and withstood 6 hours boiling in 9% sulfuric acid.

Example 10.C0ndensati0n of ethylene-bis-(Z-methoxy-4-hydroxymethylphenyl) ether to a molding compound Five parts of theproduct of Example 5 was dissolved in 380 parts of boiling water, and 3parts of hydrochloric acid was added. The mixture was stirred atrefluxing temperature for 2 /2 hours. The mixture became cloudy and anoil separated which gradually solidified. The product was removed byfiltration. It was a thermoplastic mixture which softened at 50 C.

Example 11.M0lding Three grams of the product described in Example 10was placed in a cylindrical stainless steel mold having across-sectional area of 0.787 sq. in. The mold was heated to 200 C. overa period of 40 minutes, and a pressure of 8345 pounds per sq. in. wasapplied. The mold was allowed to cool under pressure. The product was aclear, almost colorless molded disk which would take a high polish andcould be easily machined. It was insoluble in "all organic solvents andresisted the action of mineral acids. It was completely infusible.

Example 12.-C0ndensati0n 0f tetramethylene-bis-(Z-metlzoxy-4-hydroxymethylphenyl) ether The product of Example 6 washeated 2 hours at 175-- 250 C. The molten material boiled during theheating and became progressively more viscous. On cooling, a hard glassyresin remained. A small amount of this material was dissolved indimethyl formamide and coated on a glass plate. It was dried in an ovenat C. and then heated for one hour at C. The product did notmeltolselogv 300 C. and was resistant to 10% sulfuric acid at 1 Example]3.Condensati0n of bis-(2-meth0xy-4- hydroxymethylphenoxyethyl) etherExample 14.-- -Ethylene di-ethylvanillin ether ('1) CzHs (321150 Amixture of 41.5 parts of ethylvanillin, 10 parts of sodium hydroxide,250 parts of water, and 23.6 parts of ethylene dibromide was placed in areaction vessel equipped with a mechanical stirring device and a refluxcondenser. The mixture was refluxed and stirred for 15 hours. At the end,of this time, a solid had separated from" the reaction mixture. Theyield was 38 parts of product melting at 176178 C. This is 85% of thetheoretical yield. Recrystallization from 200 parts of the monomethylether of ethylene glycol gave thirty parts of product melting at 177-181C. The product was ethylene dl-ethylvanillin ether.

Example 15.-Ethylene-bis-(2-ethoxy-4- hydroxymethylphenyl) ether (')CZH5Clh so HOCHr-OOCHzCHzOGCHzOH Example 16.-C0ndensati0n ofethylene-bis-(2-eth0xy4- hydroxymethylphenyl) ether Two parts ofethy1ene-bis-(2-ethoxy-4-hydroxymethylphenyl) ether was dissolved in 170parts of hot water containing 1.3 parts of hydrochloric acid. Themixture was refluxed and it became cloudy at once. After 2% hours ofrefluxing a resin had separated and was removed. This resin softened at50 C. It was ground to a powder and molded in a press at 200 C. and apressure of 6000 lbs. per sq. in. A tough disk of light color wasobtained. It did not melt at 300 C.

The products of this invention are useful for the formation of films andmolded objects. They are particularly 6 useful where the products mustwithstand high tempera tures or acid conditions.

We claim: 1. The compound represented by the formula CR; R10 HOCHr-OO-R-OQCFQOH wherein R represents one of the divalent aliphaticgroups consisting of CH2CH2, -CH2CH2CHz--, CH2CH2CH2CH2-, and

and R1 represents a radical of the group consisting of methyl and ethyl.

2. The compounds represented by the formula OCH: CHaO in which Rrepresents one of the divalent aliphatic groups consisting of -CHz-CH2,--CH2CH2--CH2, CH2CH2CH2CH2, and

No references cited.

1. THE COMPOUND REPRESENTED BY THE FORMULA